FORMULATIONS, THE PRODUCTION AND USE THEREOF, AND SUITABLE COMPONENTS

Abstract

Described herein is a formulation including (A) citric acid or an alkali metal salt of citric acid, (B) at least one graft copolymer formed from (a) at least one graft base selected from nonionic monosaccharides, disaccharides, oligosaccharides and polysaccharides, and side chains, obtainable by grafting of (b) at least one ethylenically unsaturated mono- or dicarboxylic acid and (c) at least one compound of the general formula (I)

##STR00001## where the variables are defined as follows: R.sup.1 is selected from methyl and hydrogen, A.sup.1 is selected from C.sub.2-C.sub.4-alkylene, R.sup.2 are the same or different and are selected from C.sub.1-C.sub.1-alkyl, X.sup.? is selected from halide, mono-C.sub.1-C.sub.4-alkylsulfate and sulfate, (C) a total of zero to 0.5% by weight of methylglycinediacetic acid (MGDA) and glutaminediacetic acid (GLDA) and alkali metal salts of MGDA and GLDA.

Claims

1. A formulation comprising (A) citric acid or an alkali metal salt of citric acid, (B) at least one graft copolymer formed from (a) at least one graft base selected from nonionic monosaccharides, disaccharides, oligosaccharides and polysaccharides, and side chains, obtainable by grafting of (b) at least one ethylenically unsaturated mono- or dicarboxylic acid and (c) at least one compound of the general formula (I) ##STR00009## wherein the variables are defined as follows: R.sup.1 is selected from methyl and hydrogen, A.sup.1 is selected from C.sub.2-C.sub.4-alkylene, R.sup.2 are the same or different and are selected from C.sub.1-C.sub.4-alkyl, X.sup.? is selected from halide, mono-C.sub.1-C.sub.4-alkylsulfate and sulfate, and (C) a total of zero to 0.5% by weight of methylglycinediacetic acid (MGDA) and glutaminediacetic acid (GLDA) and alkali metal salts of MGDA and GLDA.

2. The formulation according to claim 1, which is free of phosphates and polyphosphates.

3. The formulation according to claim 1, wherein compound (c) is selected from w-trimethylaminoethyl(meth)acrylatochloride.

4. The formulation according to claim 1, wherein compound (A) is selected from the trisodium salt of citric acid.

5. The formulation according to claim 1, which is solid at room temperature.

6. The formulation according to claim 1, further comprising at least one inorganic peroxide compound (D).

7. The formulation according to claim 1, further comprising at least one polymeric builder (E).

8. The formulation according to claim 1, comprising: a total of 1% to 50% by weight of compound (A), a total of 0.1% to 4% by weight of graft copolymer (B), based in each case on the solids content of the formulation in question.

9. A method for washing dishware and kitchen utensils, the method comprising using the formulations according to claim 1 for washing the dishware and the kitchen utensils.

10. A method for washing articles having at least one glass surface which has been decorated or is undecorated, the method comprising using the formulations according to claim 1 for washing the articles.

11. The method according to claim 9, wherein the washing is effected with a machine dishwasher.

12. A process for producing formulations according to claim 1, comprising mixing at least one compound (A) and at least one graft copolymer (B) and optionally one or more further ingredients (F) and optionally peroxide (D) or chlorine bleach (D) with one another in one or more steps, optionally in the presence of water, and then optionally wholly or partially removing water.

13. The process according to claim 12, wherein the water is removed by spray drying.

14. The method according to claim 10, wherein the washing is effected with a machine dishwasher.

Description

EXAMPLES

[0194] I. Production of Inventive Formulations and of Comparative Formulations

[0195] In the context of the present application, figures in % are percent by weight, unless explicitly stated otherwise.

[0196] Graft copolymer (B.1) corresponds to graft copolymers (B.4) from WO 2015/197379. It was prepared as follows:

[0197] Comonomers Used:

[0198] (a.1): maltodextrin, commercially available as Cargill C*Dry MD01955

[0199] (b.1): acrylic acid

[0200] (c.1): [2-(methacryloyloxy)ethyltrimethylammonium chloride (TMAEMC)

[0201] Preparation of Graft Copolymer (B.1)

[0202] A stirred reactor was initially charged with 220 g of (a.1) in 618 g of water and heated to 80? C. while stirring. At 80? C. the following solutions were metered in simultaneously and via separate feeds as follows:

[0203] a) an aqueous solution of 40.6 g of (c.1) in 149 g of water, within 4 hours.

[0204] b) a solution of 9.85 g of sodium peroxodisulfate in 68.0 g of water within 5 h, beginning simultaneously with the metered addition of a).

[0205] c) a solution of 32.8 g (b.1) and 36.5 g of sodium hydroxide solution (50% in water), diluted with 139 g of water, within 2 hours, beginning 2 hours after commencement of metered addition of a).

[0206] On completion of addition of solutions a) to c), the reaction mixture was stirred at 80? C. for one hour. Subsequently, a solution of 0.73 g of sodium peroxodisulfate in 10.0 g of water was added and the mixture was stirred at 80? C. for a further 2 hours. Subsequently, the mixture was cooled to room temperature and 8 g of biocide were added. A 22.4% by weight solution of graft copolymer (B.1) was obtained.

[0207] The biocide used was a 9% by weight solution of 1,2-benzisothiazolin-3-one in water-propylene glycol mixture, commercially available as Proxel? XL2 Antimicrobial. Stated amounts are tell quel.

[0208] Inventive formulations F.1 and comparative formulations C-F.2 to C-F.4 were produced by dry mixing the components according to table 1except for surfactant 1. Nonionic surfactant 1 was melted and stirred into the dry mixture and in this way distributed with maximum homogeneity. If graft copolymer (B.1) was in the form of an aqueous solution, the graft copolymer was first isolated by drying and added in solid form to the other solid components or separately as a solution to the machine dishwasher. The components of the inventive formulation F.1 and comparative formulations C-F.2 to C-F.4 are apparent from table 1.

TABLE-US-00001 TABLE 1 Composition of inventive formulation F.1 and comparative formulations C-F.2 to C-F.4 Constituent [g] F.1 C-F.2 C-F.3 C-F.4 (A.1) 35 35 35 35 (B.1) 1 0 1 (C.1) 0 0 10 10 Polymeric builder (E.1) 4 4 4 4 (D.1) 10.2 10.2 10.2 10.2 Nonionic surfactant 1 4 4 4 4 Nonionic surfactant 2 1 1 1 1 Protease 2.5 2.5 2.5 2.5 Amylase 1 1 1 1 Na.sub.2Si.sub.2O.sub.5 2 2 2 2 TAED 4 4 4 4 Na.sub.2CO.sub.3 34.5 34.5 24.5 24.5 HEDP 0.8 0.8 0.8 0.8 ZnSO.sub.4 as heptahydrate 0.2 0.2 0.2 0.2 Key: (A.1): trisodium citrate dihydrate, corresponding to active content 30.7 g (C.1): MGDA-Na.sub.3, racemic, corresponding to active content 8 g (D.1): sodium percarbonate, 2 Na.sub.2CO.sub.33 H.sub.2O.sub.2 Nonionic surfactant 1: n-C.sub.8H.sub.17CH(OH)CH.sub.2O(EO).sub.22CH(CH.sub.3)CH.sub.2On-C.sub.10H.sub.21 Nonionic surfactant 2: n-C.sub.10H.sub.21CH(OH)CH.sub.2O(EO).sub.40n-C.sub.10H.sub.21 Na.sub.2Si.sub.2O.sub.5: commercial in the form of Britesil? H 265 LC HEDP: 1-hydroxyethane-1,1-diphosphonate disodium salt Polymeric builder (E.1): random acrylic acid/2-acrylamido-2-methylpropanesulfonic acid copolymer as sodium salt, fully neutralized, comonomer ratio 70:30 (% by weight), K value 40 (Fikentscher).

[0209] II. Tests for Determination of Glass Corrosion

[0210] Machine dishwasher: Miele G 1222 SCL

[0211] Program: 65? C. (with prewash)

[0212] Ware: 3 GILDE sekt glasses, 3 INTERMEZZO schnapps glasses

[0213] For washing, the glasses were arranged in the upper dishware basket of the machine dishwasher. The dishwashing detergent used in each case was 18 g of inventive formulation or comparative formulation according to table 1. A rinsing temperature of 65? C. was used. The water hardness in each case was in the range from zero to 2? dH. 50 rinse cycles in each case were used, meaning that the program was left to run 50? in succession. The evaluation was effected by gravimetry and by visual means after 50 wash cycles.

[0214] The weight of the glasses was determined prior to commencement of the first wash cycle and after the drying after the last wash cycle. The weight loss is the difference between the two values.

[0215] As well as the gravimetric evaluation, a visual assessment of the ware after 50 cycles was carried out in a darkened chamber under light behind an aperture using a grading scale from 1 to 5; see below. Grades were determined in each case for areal corrosion/cloudiness and for linear corrosion.

[0216] The results according to table 2 were obtained.

TABLE-US-00002 TABLE 2 Glass corrosion experiments F.1 C-F.2 C-F.3 C-F.4 Weight loss of sekt glasses (mg) 10 29 56 75 Weight loss of schnapps glasses (mg) 6 16 32 46 Linear corrosion of sekt glasses L4.5 L3.0 L3.0 L3.0 Cloudiness of sekt glasses T5.0 T5.0 T4.0 T3.5 Linear corrosion of schnapps glasses L4.5 L4.0 L1.5 L1.0 Cloudiness of schnapps glasses T5.0 T5.0 T1.5 T3.0

[0217] The assessments were made according to the following scheme:

[0218] Linear Corrosion:

[0219] L5.0: no discernible lines

[0220] L4.0: slight line formation in very few regions, fine linear corrosion

[0221] L3.0: linear corrosion in a few regions

[0222] L2.0: linear corrosion in several regions

[0223] L1.0: severe linear corrosion

[0224] Cloudiness

[0225] T5.0: no discernible cloudiness

[0226] T4.0: slight cloudiness in very few regions

[0227] T3.0: cloudiness in a few regions

[0228] T2.0: cloudiness in several regions

[0229] T1.0: severe cloudiness over almost the entire glass surface

[0230] In the inspection, intermediate grades (e.g. L4.5) were also permitted.

[0231] Test Method for Inhibition of Scale

[0232] All washing tests were conducted in a Miele G1222 SCL machine dishwasher. The program with 65? C. for the wash cycle and 65? C. for the rinse cycle was selected. The tests were conducted with hardened water having a water hardness of 21? dH (Ca/Mg):HCO.sub.3 (3:1):1.35. No separate rinse aid was added, and the installed water softener (ion exchanger) was not regenerated with regenerating salt. For each rinse cycle, a dose of 18 g of the inventive formulation specified was used. At the start of every wash cycle, 50 g of a ballast soil consisting of grease, protein and starch were added.

[0233] To assess the inhibition of scale, a total of 30 successive wash tests were conducted with the same test ware. The test ware used in each wash test was stainless steel knives, blue melamine plates, drinking glasses and porcelain cups. Between every two wash cycles, there was a delay of one hour, with the machine dishwasher door closed for 10 min thereof and opened for 50 min thereof.

[0234] For each wash test, a dose of 18 g of the inventive formulation or comparative formulation specified was used. At the start of each and every wash cycle, in addition, 50 g of a ballast soil consisting of grease, protein and starch were added.

[0235] After the 30th wash cycle had ended, the test ware was inspected visually in a darkened chamber under light behind an aperture and assessed with regard to spots, streaks and film-like deposits according to a grade scale from 1 (=severe residues) to 10 (=no residues); see table 3.

TABLE-US-00003 TABLE 3 Formation of scale, spots and streaks Knives Glasses Melamine plates Porcelain F.1 6.0 5.0 6.0 5.0 C-F.2 4.0 4.0 4.3 4.7